CN103193900B - Polymerizable benzophenone photoinitiator and preparation method thereof - Google Patents
Polymerizable benzophenone photoinitiator and preparation method thereof Download PDFInfo
- Publication number
- CN103193900B CN103193900B CN201310075757.2A CN201310075757A CN103193900B CN 103193900 B CN103193900 B CN 103193900B CN 201310075757 A CN201310075757 A CN 201310075757A CN 103193900 B CN103193900 B CN 103193900B
- Authority
- CN
- China
- Prior art keywords
- benzophenone
- preparation
- polyoxyethylene glycol
- polymerizable
- macrogol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention discloses a polymerizable benzophenone photoinitiator and a preparation method thereof. The preparation method includes firstly reacting polyethylene glycol with maleic anhydride to get carboxyl-terminated polyethylene glycol, and reacting carboxyl-terminated polyethylene glycol and an epoxy benzophenone derivative with a quaternary ammonium salt catalyst to obtain a polymerizable photoinitiator containing benzophenone and polyethylene glycol. As the photoinitiator of the present invention contains ethoxylated, the photoinitiator can be used as a hydrogen donor for benzophenone, and can help to omit the addition of an amine co-initiator, thereby reducing the yellowing caused by the amine co-initiator. Intramolecular double bond can participate in polymerization and reduce the migration of the initiator after curing. The photoinitiator has a broad industrial application prospect in coatings, inks and other light-curing materials.
Description
Technical field
The present invention relates to a kind of light trigger and preparation method thereof, particularly a kind of Polymerizable benzophenone photoinitiator and preparation method thereof.
Background technology
The polyfunctional monomers such as two (methyl) acrylate carry out photopolymerization reaction can height of formation is crosslinked fast derivatized polymers, and this feature is particularly important to the field that curing speed, cured film physical strength and stability requirement are higher at industrial coating, gear division repair materials etc.
Light trigger is the key components of photocuring system, and can it is related to formula system oligopolymer and thinner when rayed become solid-state by liquid state rapidly.Its basic role feature is: initiator molecule has certain absorbing ability at ultraviolet region (250-400nm) or visible region (400-800nm), after directly or indirectly absorbing luminous energy, initiator molecule, from ground state transition to excited singlet, is altered and is jumped to excited triplet state between being; Excited singlet or triplet state experience unit molecule or bimolecular chemical action after, produce can trigger monomer polymerization biologically active fragment, these biologically active fragments can be free radical, positively charged ion, negatively charged ion or ion radical etc.Light trigger, according to the mechanism of action of produced living radical, is mainly divided into two large classes: the light-initiated body agent of cracking type, also referred to as I type light initiation system; Hydrogen-capture-type light initiator, also referred to as II type light trigger.Wherein hydrogen-capture-type light initiator is generally based on aromatic ketone structure, and they have certain photo absorption performance, in excited state and the effect of aided initiating generation bimolecular, captures the hydrogen on aided initiating (hydrogen donor), produces living radical.
Benzophenone is a kind of widely used hydrogen-capture-type light initiator, because its surface cure is good, favorable solubility, cheap and easily obtain, but it forms base through excited triplet state and aided initiating effect and swashs mixture after must absorbing luminous energy with amine aided initiating with the use of, benzophenone, through transfer transport and hydrogen abstraction reaction, produce the amine alkyl diradical initiated polymerization with higher initiating activity.But aminated compounds has toxicity and carinogenicity, and easily there is xanthochromia in the cured film causing gained by it.Constrain its application in food and drug packages etc.
Therefore, preparation feedback activity is high, does not use the Benzophenone-type light initiator of amine aided initiating to become one of the exigence in field for this reason.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, when benzophenone uses as a kind of light trigger, need and amine aided initiating with the use of, but, aminated compounds has toxicity and carinogenicity, this restrict the use of benzophenone as light trigger
For solving this technical problem, technical scheme provided by the invention is:
The invention provides a kind of polymerizable photoinitiator containing benzophenone, the chemical structure of this initiator is shown below:
Wherein R is selected from H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, C (CH
3)
3, OCH
3or OCH
2cH
3, n=3-90.
Present invention also offers a kind of preparation method of above-mentioned light trigger, as shown in Figure 1, concrete steps are schema:
A) be 1:2.1:(0.001-0.01 by the ratio of the amount of substance of polyoxyethylene glycol, maleic anhydride, catalyzer), maleic anhydride and catalyzer is added in polyoxyethylene glycol, at 40-85 DEG C, reaction 0.5-5 hour, react complete, product with diethyl ether purification by liquid extraction several, until remove unreacted maleic anhydride, the product obtained is the polyoxyethylene glycol of end carboxyl
Wherein, polyoxyethylene glycol is selected from Macrogol 200, polyethylene glycol-800, cetomacrogol 1000, Macrogol 2000, Macrogol 3000 or Macrogol 4000,
Wherein, in this step, catalyzer selects triethylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, DMF, N,N-dimethylacetamide or trolamine,
Product with diethyl ether purification by liquid extraction 3 times, realizes effect substantially;
B) be 1:2:(0.005-0.05 by the ratio of the amount of substance of the band polyoxyethylene glycol of end carboxyl, benzophenone base glycidyl ether, phase-transfer catalyst), by the polyoxyethylene glycol of band end carboxyl obtained in step a), join in benzophenone base glycidyl ether and phase-transfer catalyst, react at 60-100 DEG C, infrared spectra monitoring reaction process, until 910cm
-1the infrared signature peak of the epoxide group at place disappears, and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol,
Wherein, phase-transfer catalyst is selected from dodecyl dimethyl benzyl ammonium chloride, bromination two octadecyldimethyl ammonium, octadecyldimethyl hydroxyethyl ammonium nitrate, Tetrabutyl amonium bromide, benzyl triethylammonium chloride or tetraethylammonium bromide.
The invention has the beneficial effects as follows: this initiator includes polyoxyethylene glycol, oxyethyl group wherein can, as hydrogen donor, therefore can be avoided adding amine aided initiating, to reduce the xanthochromia and toxicity that are caused by amine aided initiating.And this initiator contains polymerisable double bond, can photopolymerization be participated in, reduce initiator transport property after hardening.
Accompanying drawing explanation
Fig. 1 is preparation method's schema of the polymerizable photoinitiator containing benzophenone of the present invention;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 2 embodiment 1;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 3 embodiment 2;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 4 embodiment 3;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 5 embodiment 4;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 6 embodiment 5;
The polymerizable photoinitiator comprising benzophenone and polyoxyethylene glycol prepared in Fig. 7 embodiment 6.
Embodiment
Embodiment 1: take Macrogol 200 as raw material
A) maleic anhydride of 2.1 moles and the catalyst of triethylamine of 0.001 mole is added in 1 mole of Macrogol 200, react 5 hours at 40 DEG C, react complete, product with diethyl ether purification by liquid extraction 3 times, remove unreacted maleic anhydride, obtain the Macrogol 200 of end carboxyl;
B) polyoxyethylene glycol of band end carboxyl will obtained in 1 mole of step a), add the benzophenone base glycidyl ether of 2 moles and the phase-transfer catalyst dodecyl dimethyl benzyl ammonium chloride of 0.005 mole, react at 60 DEG C, infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains comprising benzophenone and polyoxyethylene glycol polymerizable photoinitiator.
Its structure as shown in Figure 2.
Embodiment 2: take polyethylene glycol-800 as raw material
A) add the maleic anhydride of 2.1 moles and the catalyst n of 0.01 mole in 1 mole of polyethylene glycol-800, N-dimethylethanolamine, react 0.5 hour at 85 DEG C, react complete, product with diethyl ether purification by liquid extraction 3 times, removes unreacted maleic anhydride, obtains the polyethylene glycol-800 of end carboxyl;
B) polyethylene glycol-800 of band end carboxyl will obtained in 1 mole of step a), add the methyl benzophenone base glycidyl ether of 2 moles and the two octadecyldimethyl ammonium of phase-transfer catalyst bromination of 0.05 mole, react at 100 DEG C, infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
Its structural formula as shown in Figure 3.
Embodiment 3: take cetomacrogol 1000 as raw material
A) add the maleic anhydride of 2.1 moles and the catalyst n of 0.005 mole in 1 mole of cetomacrogol 1000, N-diethylethanolamine, at 55 DEG C, react 2.5 hours, react complete, product with diethyl ether purification by liquid extraction 3 times, remove unreacted maleic anhydride, obtain the cetomacrogol 1000 of end carboxyl;
B) cetomacrogol 1000 of band end carboxyl will obtained in 1 mole of step a), add the tertiary butyl benzophenone base glycidyl ether of 2 moles and the phase-transfer catalyst octadecyldimethyl hydroxyethyl ammonium nitrate of 0.008 mole, react at 70 DEG C, infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
Its structural formula as shown in Figure 4.
Embodiment 4: take Macrogol 2000 as raw material
A) add the maleic anhydride of 2.1 moles and the catalyst n of 0.003 mole in 1 mole of Macrogol 2000, dinethylformamide, at 65 DEG C, react 3 hours, react complete, product with diethyl ether purification by liquid extraction 3 times, remove unreacted maleic anhydride, obtain the Macrogol 2000 of end carboxyl;
B) Macrogol 2000 of band end carboxyl will obtained in 1 mole of step a), adds the propyl group benzophenone base glycidyl ether of 2 moles and the phase-transfer catalyst Tetrabutyl amonium bromide of 0.01 mole, reacts at 75 DEG C, infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
Its structural formula as shown in Figure 5.
Embodiment 5: take Macrogol 3000 as raw material
A) add the maleic anhydride of 2.1 moles and the catalyzer trolamine of 0.006 mole in 1 mole of Macrogol 3000, at 70 DEG C, react 3.5 hours, react complete, product with diethyl ether purification by liquid extraction 3 times, removes unreacted maleic anhydride, obtains the Macrogol 3000 of end carboxyl;
B) Macrogol 3000 of band end carboxyl will obtained in 1 mole of step a), add the oxethyl-diphenyl-ketone base glycidyl ether of 2 moles and the phase-transfer catalyst benzyl triethylammonium chloride of 0.03 mole, 80 DEG C of reactions, infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
Its structural formula as shown in Figure 6.
Embodiment 6: take Macrogol 4000 as raw material
A) add the maleic anhydride of 2.1 moles and the catalyst n of 0.008 mole in 1 mole of Macrogol 4000, N-N,N-DIMETHYLACETAMIDE, at 75 DEG C, react 4.5 hours, react complete, product with diethyl ether purification by liquid extraction 3 times, remove unreacted maleic anhydride, obtain the Macrogol 4000 of end carboxyl;
B) Macrogol 4000 of band end carboxyl will obtained in 1 mole of step a), adds the methoxy benzophenone base glycidyl ether of 2 moles and the phase-transfer catalyst tetraethylammonium bromide of 0.04 mole, 90 DEG C of reactions, and infrared spectra monitoring reaction process, 910cm
-1the infrared signature peak of the epoxide group at place disappears and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
Its structural formula as shown in Figure 7.
Claims (5)
1. a preparation method for the polymerizable photoinitiator containing benzophenone, is characterized in that:
The structural formula of the described polymerizable photoinitiator containing benzophenone is
Wherein, R is selected from H, CH
3, CH
2cH
3, CH
2cH
2cH
3, CH
2cH
2cH
2cH
3, C (CH
3)
3, OCH
3or OCH
2cH
3, n=3-90,
The concrete steps of preparation method are,
A) be 1:2.1:(0.001-0.01 by the ratio of the amount of substance of polyoxyethylene glycol, maleic anhydride, catalyzer), maleic anhydride and catalyzer is added in polyoxyethylene glycol, at 40-85 DEG C, reaction 0.5-5 hour, react complete, for several times, until remove unreacted maleic anhydride, the product obtained is the polyoxyethylene glycol of end carboxyl to product with diethyl ether purification by liquid extraction;
B) be 1:2:(0.005-0.05 by the ratio of the amount of substance of the band polyoxyethylene glycol of end carboxyl, benzophenone base glycidyl ether, phase-transfer catalyst), by step a) in the polyoxyethylene glycol of band end carboxyl that obtains, join in benzophenone base glycidyl ether and phase-transfer catalyst, react at 60-100 DEG C, infrared spectra monitoring reaction process, until 910cm
-1the infrared signature peak of the epoxide group at place disappears, and namely reacts complete, obtains the Polymerizable benzophenone photoinitiator containing polyoxyethylene glycol.
2. the preparation method of the polymerizable photoinitiator containing benzophenone as claimed in claim 1, it is characterized in that: step a) described in polyoxyethylene glycol, be selected from Macrogol 200, polyethylene glycol-800, cetomacrogol 1000, Macrogol 2000, Macrogol 3000 or Macrogol 4000.
3. the preparation method of the polymerizable photoinitiator containing benzophenone as claimed in claim 1, it is characterized in that: step a) described in catalyzer select triethylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, dinethylformamide, N,N-dimethylacetamide or trolamine.
4. the preparation method of the polymerizable photoinitiator containing benzophenone as claimed in claim 1, is characterized in that: step a) described in, use in the operation of extracted with diethyl ether purified product, extraction times is 3 times.
5. the preparation method of the polymerizable photoinitiator containing benzophenone as claimed in claim 1, is characterized in that: step b) described in phase-transfer catalyst be selected from dodecyl dimethyl benzyl ammonium chloride, bromination two octadecyldimethyl ammonium, octadecyldimethyl hydroxyethyl ammonium nitrate, Tetrabutyl amonium bromide, benzyl triethylammonium chloride or tetraethylammonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075757.2A CN103193900B (en) | 2013-03-11 | 2013-03-11 | Polymerizable benzophenone photoinitiator and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310075757.2A CN103193900B (en) | 2013-03-11 | 2013-03-11 | Polymerizable benzophenone photoinitiator and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103193900A CN103193900A (en) | 2013-07-10 |
| CN103193900B true CN103193900B (en) | 2014-12-17 |
Family
ID=48716729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310075757.2A Expired - Fee Related CN103193900B (en) | 2013-03-11 | 2013-03-11 | Polymerizable benzophenone photoinitiator and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103193900B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190060463A1 (en) * | 2015-11-03 | 2019-02-28 | University Of Science And Technology Of China | Bridged polyethylene glycol-aliphatic polyester block copolymer, preparation method for same, intermediate of same, and uses thereof |
| CN105732848B (en) * | 2016-02-26 | 2017-11-03 | 中山大学 | A kind of light-cured resin and hydrophilic lubrication coating and preparation method |
| CN109180928B (en) * | 2018-09-14 | 2021-02-02 | 湖北工业大学 | Preparation method of high-purity monocarboxyl-terminated polyethylene glycol |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03143911A (en) * | 1989-10-31 | 1991-06-19 | Showa Highpolymer Co Ltd | Photosensitive polymer composition |
| CN100569731C (en) * | 2006-08-08 | 2009-12-16 | 北京英力科技发展有限公司 | Phenyl benzophenone derivates and as the purposes of light trigger |
| CN101434543B (en) * | 2007-02-12 | 2011-09-14 | 北京英力科技发展有限公司 | Polyfunctional benzophenone derivates and uses as photoinitiators thereof |
-
2013
- 2013-03-11 CN CN201310075757.2A patent/CN103193900B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103193900A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6833171B2 (en) | Fluorene photoinitiators, methods for producing them, photocurable compositions having them, and use of fluorene photoinitiators in the field of photocuring. | |
| CN108586639B (en) | Photopolymerisable thioxanthone photoinitiator containing coinitiator amine and preparation method thereof | |
| CN103193900B (en) | Polymerizable benzophenone photoinitiator and preparation method thereof | |
| JP2014526959A5 (en) | ||
| CN100395267C (en) | High molecular diphenylketone photoinitiator and its prepn | |
| CN102585045B (en) | Macromolecular polymerizable photoinitiator and preparation thereof | |
| JP2018524426A5 (en) | ||
| CN103755842B (en) | A kind of side chain contains compound light trigger of hydrogen-abstraction macromole of benzophenone and preparation method thereof | |
| Gencoglu et al. | A Water Soluble, Low Migration, and Visible Light Photoinitiator by Thioxanthone‐Functionalization of Poly (ethylene glycol)‐Containing Poly (β‐amino ester) | |
| CN105273167A (en) | Applications of iron arene salt as sensitizer used for initiating photocuring of iodonium salt under visible light | |
| CN107556408A (en) | Conjugation alkynyl phenothiazines oxime ester photoinitiator and composition for visible LED light source | |
| CN102746480A (en) | Polymerizable macromolecule photoinitiator and preparation method thereof | |
| Wang et al. | Benzophenone-di-1, 3-dioxane as a novel initiator for free radical photopolymerization | |
| JP2017057249A5 (en) | ||
| Wang et al. | Novel polymeric photoinitiators with side-chain benzophenone: Facile synthesis and photopolymerization properties without coinitiator | |
| CN103193899B (en) | Hydrogen-abstraction compound photoinitiator and preparation method thereof | |
| CN108084384A (en) | A kind of polyurethane-type polymeric diphenylmethane ketone photoinitiator | |
| CN104262511A (en) | Novel polymerizable coinitiator and UV-curable composition | |
| CN105237689A (en) | Digital light procession photocuring material and preparing method thereof | |
| CN105218708A (en) | A kind of visible light initiation system causing free radical, cationoid polymerisation | |
| CN105153329B (en) | Acetophenone type photoinitiators using fluorene as conjugated structure as well as preparation method and application of acetophenone type photoinitiators | |
| JP2015021045A (en) | Optical three-dimensional contouring resin composition consisting of cyclic ether group-containing (meth)acrylate | |
| Kahveci et al. | Photo‐induced cross‐linking of divinyl ethers by using diphenyliodonium salts with highly nucleophilic counter anions in the presence of zinc halides | |
| US20170073436A1 (en) | Light induced free radical and/or cationic photopolymerization method | |
| CN101962494B (en) | Spray painting UV primer without volatile organic compounds and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Yalan Inventor after: Wang Kemin Inventor after: Lu Yuhui Inventor after: Yu Qiang Inventor before: Wang Kemin Inventor before: Lu Yuhui Inventor before: Yu Qiang |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WANG KEMIN LU YUHUI YU QIANG TO: ZHANG YALAN WANG KEMIN LU YUHUI YU QIANG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141217 Termination date: 20210311 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |